If you're not an experienced web developer then web forms provides a familair programing model to desktop development such as vb6 or winforms and so it's a fast way to get into web programming. It hides many of the details of web programming which can be both good and bad. As you get to be a better web developer this becomes a problem because web forms provides a huge abstraction model and it's a lot of work th wade thru the abstraction model to do the things you want.

As for MVC, it's "closer to the metal" of web programming but expects you as a developer to be more understanding of web programming. This means you should know modern HTML, CSS and JavaScript to really get the most of MVC.

So... short answer... it depends. Do you "care" about web development? If you don't really care about the details, then Web Forms is a good transition given your background. If you really want to get into web development and do it well, then it means there might be more of a learning curve but MVC will give you the control to do things right.

As for EF... it's the standard microsoft framework for doing DB access these days.